A dibromobismuthine and a dibromostibine that bear 4-tBu-2,6-[CH­(SiMe3)2]2-C6H2 (Tbb) groups were reduced with 2,3,5,6-tetramethyl-1,4-bis­(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene to afford the corresponding stable dibismuthene (TbbBiBiTbb) and the distibene (TbbSbSbTbb), respectively. The only byproducts obtained were easily removable tetramethylpyrazine and bromotrimethylsilane. Importantly, inorganic salts were not generated in this reduction: i.e., this is a unique inorganic-salt-free method for the synthesis of compounds with multiple bonds between heavier main-group elements.

) respectively, which signifies the potential of these oxidovanadium(V) complexes to stimulate research for the synthesis of a better catalyst.

Tetrylones (ylidones) represent a class of zero-valent group 14 compounds with the general formula EL (E=C, Si, Ge, Sn, or Pb; L=neutral σ-donating ligand), wherein the tetrel atom, E(0), possess its four valence electrons in the form of two electron lone pairs, and is moreover coordinated by two ligands (L) via donor-acceptor interactions (L→E←L). This review focuses on the synthesis, structure, reactivity, and computational examination of the isolable heavier tetrylones (Si, Ge, Sn) that have been discovered recently. A comprehensive review on carbone chemistry is beyond the scope of this review. It should also be noted that tetrylones contain two different types of lone pairs, that is, one that exhibits p-type and one that exhibits s-type characteristics. Different behavior should thus be expected when these lone pairs react with Lewis acids.

Selective formation of 4-phosphanylated 1,2-dialkyl imidazole-2-thiones 3a-f has been obtained via a lithiation followed by phosphanylation reaction. The reactivity of 3a-f was examined towards oxidation and complexation reactions. All products were unambiguously characterized by elemental analyses, spectroscopic and spectrometric methods including X-ray analysis (3a, 3b, 4b, 4d, 5b, 6a and 6d).

Matter of opinion: The novel zwitterion 1 has been synthesized and studied theoretically and also converted into anionic NHCs 2. The former can also be described as a phosphinidene adduct of an abnormal N-heterocyclic carbene (1') and, in the same vein, the latter represents a phosphinidene adduct of an anionic N-heterocyclic dicarbene (2').

Synthesis of 1,1'-bifunctional aminophosphane complexes 3 a-e was achieved by the reaction of Li/Cl phosphinidenoid complex 2 with various primary amines (R=Me, iPr, tBu, Cy, Ph). Deprotonation of complex 3 a (R=Me) with potassium hexamethyldisilazide yielded a mixture of K/NHMe phosphinidenoid complex 4 a and potassium phosphanylamido complex 4 a'. Treatment of complex 3 c (R=tBu) and e (R=Ph) with KHMDS afforded the first examples of K/NHR phosphinidenoid complexes 4 c and e. The reaction of complex 3 c with 2 molar equivalents of KHMDS followed by PhPCl afforded complexes 5 c,c', which possess a P N-ring ligand. All complexes were characterized by NMR, IR, MS, and microanalysis, and additionally, complexes 3 b-e and 5 c' were scrutinized by single-crystal X-ray crystallography.

1-Alkyl-3-methyl-4-diphenylphosphoryl-imidazolium hydrogensulfate (4a,b) (a: R(1) = R(2) = Me; b: R(1) = (i)Pr, R(2) = Me) and 1-alkyl-3-methyl-4,5-bis(diphenylphosphoryl)imidazolium hydrogensulfate (6a,c) (c: R(1) = (n)Bu, R(2) = Me) were obtained selectively and in good yields by oxidative desulfurization of 1-alkyl-3-methyl-4-diphenylphosphino-imidazole-2-thiones (2a,b) and 1-n-butyl-3-methyl-4,5-bis(diphenylphosphoryl)imidazole-2-thione (3c) or 1,3-dimethyl-4-diphenylthiophosphoryl-5-diphenylphosphino-imidazole-2-thione (5a), respectively, with hydrogen peroxide. Synthesis of phosphoryl functionalized imidazol-2-ylidene complexes of group VI metal pentacarbonyls (7a-9a) and (10b-12b) and bis(phosphoryl) functionalized imidazol-2-ylidene complexes of group VI metal pentacarbonyls (13c-15c) and (16a) with low steric demand (methyl, isopropyl, n-butyl) at both N-centers was achieved through deprotonation of imidazolium salts (4a,b) and (6a,c), respectively,-having HSO(4)(-) as a counterion-with potassium tert-butoxide followed by rapid addition of metal pentacarbonyl acetonitrile complexes [M(CO)(5)(CH(3)CN)] (M = Cr, Mo, W). The products were unambiguously characterized by elemental analyses, spectroscopic and spectrometric methods, and in addition, by single-crystal X-ray structure studies in the cases of 4b, 8a, 15c, and 16a; the latter two reveal imidazole ring bond distance alternation in contrast to 8a.

Metalation reactions were studied of a sterically demanding imidazole derivative, namely, 1-tert-butylimidazole (1), with different metalation reagents and subsequent reaction with diphenylchlorophosphane. The reaction product, 1-tert-butyl-2-diphenylphosphino-imidazole (2), was subjected to oxidation and complexation reactions to yield the corresponding products Ph(2)(Imi)P-E (E = O (3), S (4), Se (5), W(CO)(5) (8)) and in the case of borane-THF the N-BH(3) coordination product 10 was obtained. The analytical data of the new compounds are discussed, including X-ray diffraction studies of 3-5.